JPS62283117A - Production of oil-modified phenolic resin - Google Patents

Abstract

PURPOSE:To obtain an oil-modified phenolic resin suitable for electronic apparatus, by converting a phenolic resin modified with oiticica oil to a resol using ammonia as a catalyst and continuing the reaction by the addition of large excess of paraformaldehyde compound to the system in the presence of a tertiary amine catalyst. CONSTITUTION:A phenolic compound is made to react with oiticica oil in the presence of an acidic catalyst (e.g. hydrochloric acid) and then with a formaldehyde compound (e.g. paraformaldehyde) in a lower aliphatic alcohol solvent (e.g. methanol) in the presence of ammonia. The objective resin can be produced by adding a formaldehyde compound to the reaction system in the presence of a tertiary amine catalyst (e.g. triethylamine) and reacting the components. The molar ratio of the phenolic compound to the formaldehyde compound is maintained at >=1.6 as a whole.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention Field of Industrial Application The present invention relates to a method for producing an oil-modified phenolic resin suitable for producing phenolic resin laminates conveniently used in electronic devices.

BACKGROUND OF THE INVENTION Conventionally, phenolic resin modified with tung oil has been widely used for phenolic resin laminates or phenolic resin steel-clad laminates. Since tung oil has conjugated double bonds and reacts well with phenols, its modified phenolic resin can be used for excellent magnetic performance and punching processing. A laminate with E is obtained.

The above-mentioned tung oil is naturally produced, and there are problems in that the yield is affected by the weather, the price fluctuates significantly, and it is difficult to secure a stable raw material. Therefore,
Oiticica oil is being considered as a substitute for tung oil.

Oiticica oil is a stable raw material in terms of price, and has the same reactivity as tung oil because its main component is lycanic acid. shows.

Problems to be Solved by the Invention 1. Unlike pyricanic acid tz and Ot-eleostearic acid, it has a keto group in its molecular chain.

The reactivity with phenols is different. In addition, Oiticica oil has a higher content of saturated fatty acids and higher viscosity than Tung oil, and is also different in its compatibility with phenolic resins. For example, when a resole is produced by reacting a oyster oil/phenol adduct with formaldehyde in the presence of a basic catalyst, the compatibility of the resin composition is poor, making it difficult to obtain a transparent and uniform cured product, and the resin viscosity However, it has the disadvantage that it is generally poor in impregnating the base material.

The purpose of the present invention is to provide an oil-modified phenolic resin modified with Oiticica oil, which has good impregnation properties into a base material and is suitable for manufacturing TSM boards.

Means for Solving the Problems In the present invention, phenols and Oiticica oil are first reacted in the presence of an acidic catalyst to form an Oiticica oil-phenol adduct.Next, a lower aliphatic alcohol is reacted in the presence of an ammonia catalyst. After reacting formaldehydes in a bath medium, a large excess (total molar ratio of phenols/formaldehydes of 1.6 LLh) of formaldehydes with a two-part tertiary amine catalyst is added to form a resol. This is a method for producing an Eitizocca oil f-based phenolic resin.

Function The Oiticica oil-modified phenol resin according to the present invention 1 can be used as a basic catalyst by performing the resolization reaction in a lower aliphatic alcohol solvent to homogenize the reaction system and suppress rapid polymer formation. First, we proceeded to polymerize the oiticica oil-phenol adduct in the presence of ammonia, and then proceeded with the reaction with a large excess of formaldehyde in the presence of a tertiary amine catalyst.

It becomes an oil-modified phenolic resin with many methylol groups. This is because the curing speed is fast and the impregnating properties of the base material are excellent.

In the presence of a tertiary amine catalyst, when Y is added in large excess of phenols (2 to 2 - formaldehydes), the total molar ratio of formaldehydes to phenols is 1.
When it is smaller than 6, the raw 5yC of methylolphenols in the reaction system is small.

It is not suitable as it has poor impregnating properties into the base material.

Examples The phenols used in the present invention include coal slag, cresol,
Quinlenol, butylphenol, octylphenol, nonylphenol, cashnut oil, urushiol, resol//, naphthol, and the above-mentioned phenols such as novolak, bisphenol Ar, etc.The acidic catalyst used in the present invention includes hydrochloric acid, iK acid, These include inorganic acids such as toluene sulfonic acid, and organic acids such as toluene sulfonic acid and kiln sulfonic acid.

Oiticica oil obtained in the presence of acidic catalyst - addition of phenols? J is then reacted with formaldehydes in a lower aliphatic alcohol solvent in the presence of an ammonia catalyst, and furthermore, a large amount of formaldehydes is added in a third plate under an aqueous solvent to proceed with the reaction. become The tertiary amines used at this time include: triethylamine, trimethylamine, benzyldimethylamine, 2°so4.6-tos(trimethylaz2methyl)phenol,
2-, methylimidazole, 2-phenylicoxol, 2-ethyl, 4-methyligodazole and the like are suitable.

For formaldehyde, it has advantages such as homogenizing the reaction system, omitting the vacuum dehydration step after the resolization reaction, and reducing the amount of basic catalyst added.
It is preferred to use 80-90% paraformaldehyde of 'ix.

The molar ratio of formaldehydes to phenol mE is 1.1 to 1.3 molar in the resolization under an ammonia catalyst (preferably; then, the formaldehyde added in large excess under a tertiary amine catalyst is in total phenol mE). A suitable amount is 1.6 mol or more per 1.6 moles or more.During the resolization reaction in a lower aliphatic alcohol solvent under an ammonia catalyst, the above phenols may be added or added depending on the fee. The lower aliphatic alcohol used in the present invention is preferably one having 3 or less carbon atoms, such as methanol or ethanol propyl alcohol.

After impregnating and drying a base material such as cotton linter paper or kraft paper with the present invention's oil-based phenol side fat, the required number of sheets are stacked and copper foil is applied on one or both sides as necessary. Is it a laminated board or steel-clad laminated board made by bundling and heating and pressurizing it? :obtain. In addition, when impregnating the base material with the oil-modified phenol resin according to the present invention, mixing the initial condensate of water and phenolic resin),
Alternatively, it is also possible to use a base material pre-impregnated with the above-mentioned initial condensate.

Example 1 Add 0.5t of paratoluenesulfone tlR to phenol 500F and 500t of Oiticica oil, and heat to 95-100°C.
The mixture was reacted for 120 minutes to obtain an oiticica oil-phenol adduct. Subsequently, methanol 5(]?, ammonia water 10?, and 85% formaldehyde 5725f were added, and after reacting at 95-1()0℃ for 2 hours, triethylamine 309.85%, formaldehyde 10%
Add 0f.

A resol varnish was obtained by reacting at 80 to 85°C for 5 hours.

This varnish was diluted with methanol to obtain a phenolic resin varnish modified with Oiticica oil having a concentration of 50%. Kraft paper was impregnated with the phenolic resin varnish modified from oil and dried to obtain coated paper with a reduced fat content of 48%. This 8-ply coated paper and 35μ copper foil with adhesive on one side? :Stack, temperature 1
60℃, pressure 100Kff//lI! Il: Heat and pressurize for 50 minutes to a thickness of 1. A G w4 copper clad laminate was obtained. Its performance is shown in the table below.

Comparison flJ ] Phenol 500, Oiticica oil 50? Paratoluene sulfone! 0.5P at 95-100℃
React for 20 minutes and add Oitizocca oil-7JO with phenol.
I got something. 50 tons of methanol, 3 tons of ammonia water
0P, add 853 rose formaldehyde 2251, 9
After incubating at 5 to 100°C for 6 hours, it was concentrated under reduced pressure.
It was diluted with a toluene/methanol-50/s O solvent to obtain a phenolic oil-modified phenol impregnated varnish with a fallen fat content of 50%.

Using the above varnish, a 1.6 m thick copper-clad laminate was obtained in the same manner as in Example 1. Table 1 shows the performance of 7.

Table 1 □□□□□□□□□■ *1 Varnish volatilization rate...] Varnish solid content that volatilizes at 60°C/2 minutes Effect of the invention The Oiticica oil-modified phenolic resin according to the present invention uses an ammonia catalyst. By converting it into a resol, polymerizing it, and then adding a large excess of paraformaldehyde under a tertiary 2-catalyst to further proceed with the reaction, it is possible to obtain a varnish with a large number of methylol groups in the system. The obtained varnish has a plasticizing effect and is capable of impregnating the base material as described above, and by using it, it is possible to obtain a laminate with excellent cis properties, water resistance, and punching workability. can.

In addition, as shown in Table 3, productivity such as f2 and varnish yield of 1 is excellent, and the industrial value is extremely high.

Patent owner Shin-Kobe Electric Co., Ltd.

Claims (1)

[Claims] After reacting phenols and oiticica oil in the presence of an acidic catalyst, formaldehydes are reacted in a lower aliphatic alcohol solvent in the presence of an ammonia catalyst, and then a third reaction is performed.
Formaldehydes were added in large excess in the presence of a class amine catalyst (total phenol/formaldehyde molar ratio of 1.
6 or more) and reacting the resin.